Antimicrobial polymeric quaternary ammonium salts

ABSTRACT

In one aspect, compounds, methods of using them, compositions comprising such compounds, and uses of such compositions. 
     These objects, and others which will become apparent from the following disclosure, are achieved by the present invention which comprises in one aspect compounds of the formula ##STR1## wherein R is alkyl, cycloalkyl, aryl, substituted aryl, alkaryl optionally substituted on the aryl portion or aralkyl optionally substituted on the aryl portion, R having up to 20 carbon atoms and is optionally branched, and 
     A is (CH 2 ) p , (CH 2 ) q  --O--(CH 2 ) r , or (CH 2 ) q  --S--(CH 2 ) r , 
     wherein p=2 to 8, q=1 to 8, and r=1 to 8. 
     R 1  =--(CH 2 ) m  --, --(CH 2  CH 2  --O) n  --CH 2  CH 2  --, or --(CH 2  CH 2  CH 2  --O) n  --CH 2  CH 2  CH 2  --. 
     In another aspect, the invention comprises polymers of the formula ##STR2##

This is a divisional of application Ser. No. 637,085, filed Jan. 3, 1991, now U.S. Pat. No. 5,149,524.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to control of microorganisms.

2. Description of the Prior Art

The self-condensation of various bromoalkylamines has been studied since 1906 starting with bromoethyldimethylamine which reacted with itself to form a cyclic quat with a 6-membered ring, reported by Knorr and Roth,, Ber., 39, 1425 (1906).

Kern and Brenneisen, J. Prakt. Chem., 159, 193 (1941 ), reported another type of linear polyquat using di-tertiary amines to react with di-halides. Both starting materials are readily available.

Carothers, JACS, 51, 2548 (1929) suggested a polymeric quat from bromoalkylamines.

Marvel et al., JACS, 49,2299 (1927) suggested intracyclization of bromobutyldimethylamine to form cyclic quats. Other reports by Marval and colleagues were published in JACS, 52, 287 (1930), JACS, 55, 753 (1933), JACS, 55, 1977 (1933), JACS, 56, 725 (1934), and JACS, 57, 1127 (1935).

Ritter, U.S. Pat. No. 2,261,002 and Searle et al, U.S. Pat. No. 2,271,378, both assigned to Dupont, disclosed polymeric quats having pesticidal utility (fungicides, insecticides, disinfectants).

Rembaum, et al, Polymer Letters, 6, 159 (1968), named both type polyquats as "aliphatic ionenes."

Noguchi, et al, Poly. Prepr. ACS Dev. Polym. Chem., 10, 718 (1969) reviewed cyclic, linear and polymeric ammonium salts.

Bortel et al, published studies on "Chloro-ionenes"; "Chloro-lonenes with Ether Bonds in the Backbone Chain. Determination of Rate Constants, Orders of Reaction and Molecular Weights," Makromol. Chem., 182, 3099-3108 (1981), and "Chloro-lonenes from Dichlorides and tertiary diamines," Makromol. Chem., 188, 2019 (1987).

SUMMARY OF THE INVENTION

It is an object of the present invention to provide new compounds for controlling microorganisms.

A further object is to provide methods of making such compounds, methods of using them, compositions comprising such compounds, and uses of such compositions.

These objects, and others which will become apparent from the following disclosure, are achieved by the present invention which comprises in one aspect compounds of the formula ##STR3## wherein R is alkyl, cycloalkyl, aryl, substituted aryl, alkaryl optionally substituted on the aryl portion or aralkyl optionally substituted on the aryl portion, R having up to 20 carbon atoms and is optionally branched, and

A is (CH₂)_(p), (CH₂)_(q) --O--(CH₂)_(r), or (CH₂)_(q) --S--(CH₂)_(r),

wherein p=2 to 8, q=1 to 8, and r=1 to 8.

R₁ =--(CH₂)_(m) --, --(CH₂ CH₂ --O)_(n) --CH₂ CH₂ --, or --(CH₂ CH₂ CH₂ --O)_(n) --CH₂ CH₂ CH₂ --

In another aspect, the invention comprises polymers of the formula ##STR4##

In another aspect of the invention comprises a process comprising reacting a monoalcohol of the formula

    X--R.sub.1 --OH                                            (I)

wherein R₁ =--(CH₂)_(m) --, --(CH₂ CH₂ --O)_(n) --CH₂ CH₂ --, or --(CH₂ CH₂ CH₂ --O)_(n) --CH₂ CH₂ CH₂ -- in which m=7 to 24, n=1 to 10, and wherein X=Br, Cl, or OSO₂ R wherein R is alkyl, cycloalkyl, aryl, substituted aryl, alkaryl optionally substituted on the aryl potion or aralkyl optionally substituted on the aryl portion, R having up to 20 carbon atoms and is optionally branched with a molar excess of secondary ring amine of the formula ##STR5## wherein A is (CH₂)_(p), (CH₂)_(q) --O--(CH₂)_(r), or (CH₂)_(q) --S--(CH₂)_(r), or (C₁₋₃)alkyl substituted analogous thereof, wherein p=2 to 8, q=1 to 8, and r=1 to 8 to form a compound of the formula ##STR6## and reacting (Ill) with X'SO2R wherein R is alkyl, cycloalkyl, aryl, substituted aryl, alkaryl optionally substituted on the aryl potion or aralkyl optionally substituted on the aryl portion, R having up to 20 carbon atoms and is optionally branched and wherein X' is Cl or Br, to produce a monomer of the formula ##STR7##

A further aspect of the invention is the process comprising polymerizing monomer (IV) to produce a polymer of the formula ##STR8## wherein t=1 to about 100.

A further aspect comprises using a composition comprising the polymer and/or monomer compounds, or the polymer and/or monomer compound itself, to protect a material selected from the group consisting of wood, paint, adhesive, glue, paper, textile, leather, plastics, cardboard, lubricants, cosmetics, food, caulking, feed and industrial cooling water from microorganisms.

DETAILED DESCRIPTION OF THE INVENTION AND THE PREFERRED EMBODIMENT

The compounds of the invention are of formulae IV and V as set forth above. The more preferred embodiments are the polymers of formula V wherein R₁ is --(CH₂)_(m) --, m is 11 or 12, R is p-toluene, A=(CH₂)_(p), wherein p=4, 5, or 6 and t=about 4 to 10. ##STR9## is preferably piperidine, pyrrolidine, or hexamethyleneimine.

The polymer and monomer compounds are useful for controlling plant pathogenic microbes with low toxicity to said plant. This controlling is achieved by applying the polymers of formula V or compositions comprising the polymers to a plant which is subject to pathogenic microbes. An especially effective use is when the plant pathogen being controlled is of the genus xanthomonas.

The polymers of formula V can also be used in topical sprays along with an adjuvant, for example EDTA or sodium dodecyl alcohol.

As stated above, compositions comprising a polymer according to formula V and either an agronomically acceptable carrier, a cosmetic agent, a cutting oil, a soap or synthetic detergent, a stabilizer, a film forming material, or the like, have a wide range of utility for protecting against or controlling microorganisms from a wide variety of classes including fungus, bacteria, algae, viruses and yeasts. The preferred utilities of the compositions are to protect wood, paint, adhesive, glue, paper, textile, leather, plastics, cardboard, lubricants, cosmetics, food, caulking, feed and industrial cooling water from microorganisms.

We discovered that the polymers of the invention are very active. The polymers, contrary to related commercial quat biocides, do not lose activity in the presence of organic matter; they are non-corrosive to metals and are non-foaming.

The following lists specific industries and applications of the compounds or compositions:

    ______________________________________                                         Industry      Application                                                      ______________________________________                                         Adhesives, sealants                                                                          adhesives                                                                      caulks                                                                         sealants                                                         Agriculture/food chain                                                                       adjuvant preservation                                                          agricultural active ingredient                                                 agricultural chemical preservative                                             agricultural formulations preservation                                         animal feed preservation                                                       dairy chemicals                                                                fertilizer preservation                                                        food preservation                                                              food processing chemicals                                                      grain preservation                                                             post-harvest produce protection                                                sugar processing                                                               tobacco                                                          Construction products                                                                        asphalt/concrete                                                               cement modifiers                                                               construction products                                                          roof mastics                                                                   synthetic stucco                                                               wall mastics                                                                   joint cement                                                     Cosmetics and toiletries                                                                     cosmetics                                                                      raw materials for cosmetics, toiletries                                        toiletries                                                       Disinfectants, antiseptics                                                                   antiseptic                                                                     disinfectant                                                     Emulsions, dispersions                                                                       aqueous dispersions                                                            dispersed pigments                                                             latex                                                                          photographic emulsions                                                         pigment slurries                                                               polymer lances                                                   Formulated household                                                                         fabric softeners                                                 products      polishes                                                                       waxes                                                                          hand dish detergents                                                           raw materials                                                                  liquid detergents                                                              hand soaps                                                       Industrial processing,                                                                       electrodeposition paint, baths, rinses.                          misc          electrodeposition pretreatment, post                                           rinses                                                                         industrial fluids preservation                                                 pasteurization baths                                                           process aid preservation                                         Industrial water                                                                             air washers                                                      treatment     cooling towers                                                                 cooling water                                                                  water cooling                                                                  preservation/treatment of wooden                                               cooling tower slats and structural                                             members                                                                        can warmers                                                                    brewery pasteurization                                                         closed loop water cooling systems                                Laundry       household laundry products                                                     laundered goods                                                                laundry wash water                                                             sanitizers-laundry                                               Leather,      leather and hide                                                 leather products                                                                             leather and hide product                                         Lubricants,   automotive lubricants and fluids                                 hydraulic aids                                                                               conveyor lubricants                                                            greases                                                                        hydraulic fluids                                                               lubricants                                                       Medical devices                                                                              diagnostic enzymes                                                             diagnostic kits                                                                medical devices                                                  Metalworking &                                                                               cutting fluids                                                   related app's metal cleaning                                                                 metalworking fluids                                              Odor control  air conditioning                                                 (active ingredient)                                                                          animal bedding                                                                 cat litter                                                                     chemical toilet prep'ns                                                        deodorizers                                                                    humidifiers                                                                    industrial deodorants                                                          sanitary formulations                                                          toilet bowls                                                     Paints and    emulsions                                                        coatingscoating                                                                              paints                                                           Paper and wood pulp,                                                                         absorbant materials of paper and wood                            their products                                                                               pulp                                                                           packaging materials of paper and wood                                          pulp                                                                           paper                                                                          paper products                                                                 paper treatment                                                                soap wrap                                                                      wood pulp                                                                      wood pulp products                                               Paper mill    paper mill slimicides                                                          pulp and paper slurries                                          Petroleum refining, fuels                                                                    aviation fuels (jet fuel, aviation gas)                                        crude oils                                                                     burner, diesel and turbine fuel oils                                           coal slurries                                                                  diesel fuel additives                                                          diesel fuels                                                                   fuels                                                                          gasoline                                                                       heating oils                                                                   hydrocarbons                                                                   kerosene                                                                       liquefied petroleum gas                                                        petrochemical feedstocks                                                       petroleum products, storage,                                                   transportation and production                                                  recycled petroleum products                                                    residual fuel oils                                                             turbine oils                                                     Photographic chemicals                                                                       photographic processing - wash water,                            and process   rinses                                                                         photoprocessing                                                                photoplate processing chemicals                                                (developers, stabilizers etc)                                    Printing      fountain solutions (printing)                                                  ink components (pigments, resins,                                              solvents, etc)                                                                 inks                                                             Sanitizers (active)                                                                          sanitizers                                                                     sanitizers-dairy                                                               sanitizers-dental                                                              sanitizers-fermentation                                                        sanitizers-food preparation                                                    sanitizers-food processing                                                     sanitizers-medical                                                             sanitizers-rendering                                                           sanitizers-veterinary                                            Soaps, detergents,                                                                           cleaners                                                         cleaners      detergents                                                                     household cleaners                                                             industrial cleaners                                                            liquid soaps                                                                   oil and grease remover                                                         powdered soaps                                                                 raw materials for cleaning products                                            soaps                                                                          surfactants                                                      Textiles, textile products                                                                   bonded fabrics                                                                 burlap                                                                         canvas                                                                         canvas goods                                                                   carpet backing                                                                 carpets                                                                        clothing                                                                       coated fabrics                                                                 curtains                                                                       draperies                                                                      engineering textiles                                                           fibers                                                                         geotextiles                                                                    goods made of textiles                                                         knitted fabrics                                                                nets                                                                           nonwoven fabrics                                                               rope                                                                           rugs                                                                           textile accessories                                                            textile products                                                               textiles                                                                       upholstery                                                                     woven fabrics                                                                  yarn                                                             Textile processing                                                                           dye fixatives                                                                  dyes                                                                           fiber lubricants                                                               hand modifiers                                                                 sizes                                                                          textile processing fluids                                        Therapeutic (active or                                                                       animal health/veterinary                                         preservative) aquaculture                                                                    dental                                                                         human health                                                                   pharmaceutical/therapeutic                                       Water purification                                                                           charcoal beds                                                                  deionization resins                                                            filters                                                                        membranes                                                                      reverse osmosis membranes                                                      ultrafilters                                                                   water purification                                                             water purification pipes, tubing                                 Wood applications                                                                            lazures (wood stains)                                                          wood                                                                           wood products                                                    Miscellaneous alcohols                                                                       bedding incorporating water or gets                                            ceramic                                                                        contact lens cases-leaching                                                    electronic circuitry                                                           electronics chemicals                                                          enzymes-food production                                                        enzymes                                                                        enzymes-industrial                                                             gel cushions                                                                   marine antifoulants                                                            mildewcides                                                                    wood                                                                           plastics                                                                       laundry                                                                        mining                                                                         natural rubber latex                                                           oil field injection waters including                                           enhanced recover injection fluids,                                             drilling, fracturing and completion                                            fluids                                                                         pipes                                                                          plastics                                                                       polymer systems                                                                polymers and resins (synthetic and                                             natural)                                                                       reagent preservation                                                           rubber                                                                         rubber products                                                                skin remover                                                                   solid protective/decorative films                                              stains                                                                         swimming pools                                                                 waste treatment                                                                water beds                                                       ______________________________________                                    

The amounts of the compound to be used depend on the application. The useful amounts for a particular application are similar to amounts used for other microbiocide compounds.

The compound can be used in combination with other microbicides. The term "microbicide" is considered equivalent to "antimicrobial" as used herein.

Suitable methods of application of compounds of formula I to control fungi, bacteria, algae, viruses, yeasts, and the like are in amounts and with carriers, etc., as well known in the art.

The following examples are presented to illustrate a few embodiments of the invention. All parts and percentages are by weight unless otherwise indicated.

The following procedures were used to evaluate biological activity:

This test is run on bacteria in synthetic hard water without the benefit of nutrients. A 1.0% slant tube is used to grow Ps.fl. which is washed with four ml of sterile water. This wash is diluted to a density of 60 to 80 NTU.

The above inoculum is diluted with SHW, 1.5 ml inoculum to 100 ml of SHW. This seeded SHW is used to fill the microtiter wells.

1. To 100 ml of sterile Synthetic Hard Water (SHW) add 1.5 ml of inoculum from the 60-80 NTU slant wash and mix well.

2. Using an 8 channgel micro pipet, transfer 100 μl of the mix from a single reservoir tray to each well of the microtiter plate. Add an additional 90 μl to the first row of wells, bringing the total in row 1 to 190 μl.

3. To the top well in each column add 10 μl of compound prep, so that 6 compounds, a blank, and a standard are located along the A row. The 10 μl of 5,000 ppm prep plus 190 μl of Ps.fl. SHW make a compound concentration 250 ppm.

4. Using an 8 channel micropipet, mix and transfer 100 μl from each well of row 1 to the next row, making a 1:1 dilution to 125 ppm of the 6 compounds and standard in row 2.

5. Repeat this to make successive 1:1 dilutions to the bottom row.

6. Allow the plate to incubate for 4 hr.

7. Prepare a microtiter plate containing 100 μl TSB in each well.

At hour hours use the Clonemaster to transfer 5 μl from each well of the SHW plate to the TSB plate for recovering living cells.

8. Incubate this recovery plate for 24 hr. at 30° C. before noting the concentration at which each compound killed the cells in the SHW plate, resulting in clear wells or no growth in the corresponding wells of the TSB recovery plate.

A. Total Kill Test Protocol

1. Grow Psae in triptocase soy broth

2. Put 100 μl/10 ml of 0.85% saline contained in 0.05M N-tris[hydroxymethyl]methyl-2-amino ethanosulfonic acid buffer at pH 7.0.

3. Fill microtiter plates with 100 μl of #2 except top wells--they contain 190 μl of #2.

4. Add 10 μl of test compound at time zero then serial dilute by 2×.

5. Using a 96 pin (1.5 μl each pin) Dynatech inoculator recover to triptocase soy broth agar plate by touching agar with 96 pins.

6. Incubate at 30° C. for 48 hours.

7. Read the pin spot where no growth occurred. This is the point that total kill occurs with a certain concentration/test compound at a certain time.

C. Speed of Kill ("SOK") tests were run as follows:

1. Grow Psae or Saur or Sal chlo on triptocase soy broth agar slants.

2. Wash slants with 10 ml 0.85% saline, 0.05 N-tris[hydroxymethyl]methyl-2-amino ethanosulfonic acid buffer pH 7.0

3. Pour #2 into sterile vial.

4. Vortex #3.

5. Add 10 ml of #4 to sterile 2 oz jar with a stirring bar.

6. Remove 100 ml of #5 to triptocase soy broth for zero time call count.

7. Add test compound at desired concentrations.

8. With time intervals remove adjuvants to 100 ml of sterile triptocase soy broth.

9. Do cell counts of #8 by pour plating in sterile triptocase soy broth agar.

10. Incubate agar plates at 30° C. for 72 hours.

11. Calculate log reduction of viable cells.

D. A minimum inhibitory concentration (MIC) values were obtained using a broth, two-fold serial dilution test performed as follows: A stock solution or dispersion of the test compound, typically at a concentration of 1%, is made in a 5:3:2 solvent solution of acetone, methanol, and water. A volume of the stock solution is dispensed into culture media to give an initial starting test concentration of 500 ppm compound.

When the test is ready to be done, each vessel in the dilution series, except the first vessel, contains an equal volume of compound free broth. The first vessel contains twice the volume of broth with the starting concentration of test compound. One half of the broth from the first vessel is transferred to the second vessel. After being mixed, one half the resulting volume is removed from the second vessel and transferred to the third vessel. The entire cycle is repeated sufficiently to give a series of concentrations amounting to 250, 125, 63, 31, 16, 8, and 4,2, 1, 0.5, 0.25, and 0.12 ppm

Each vessel is then inoculated with a cell suspension of the appropriate test organism. Bacteria are grown in broth; fungi on agar slants for a time and at a temperature appropriate to the species being tested; and algae are a mixture of green algae and blue-green bacteria grown in a nutrient media. At the end of the growth period, in the case of bacteria, the broth is vortexed to disperse the cells.

In the case of fungi, the spores are harvested by pipetting water onto the slant and dislodging the spores with a sterile loop. The cell/spore suspension is standardized by controlling incubation time, temperature, and the volume of the diluent. The suspension is then used to inoculate the vessels containing the broth compound.

The algae culture contains green algae and blue-green bacteria, and is obtained from a cooling tower in Spring House, Pa. The algae culture is grown in Allen's medium on a rotary shaker under flourescent room lighting. This culture is further diluted with Allen's medium and then added to the test vessel.

The vessels are then incubated at the appropriate temperature. After the incubation, the vessels are examined for growth/no growth. The minimum inhibitory concentration (MIC) is defined as the lowest concentration of compound that results in complete inhibition of growth of the test organism.

The organisms tested to demonstrate biocidal activity include:

BACTERIA:

Pseudomonas fluorescens (PSFL), gram negative

Pseudomonas aerugenosa (PSAE), gram negative

Escherichia coli (ECOL), gram negative

Staphylococcus aureus (SAUR), gram positive

FUNGI:

Aspergillus niger (ANIG)

Aureobasidium pullulans (APUL)

EXAMPLE 1 A. Synthesis of 11-(N-piperidyl)undecane-1-(p-toluene)sulfonate

11-Bromoundecanol (11.00 g., 43.79 mmole) was dissolved in 100 ml. of piperidine and heated at reflux temperature for 18 hours. The reaction mixture was allowed to cool and most of the precipitated piperidine hydrobromide was removed by filtration. The excess piperidine is removed by simple distillation and the resultant solid residue is recrystallized from ethanol and water. After drying, 10.78 g. (96.3% yield) of 1-hydroxy-11-(N-piperidyl)undecane was obtained. m.p. 62°-65° C., ¹ H-NMR (200 MHz, CDCl₃) δ=1.2-1.7 ppm, m, 24H; 2.10, broad s, 1H; 2.20-2.45, m, 6H; 3.63, t, 2H.

The 1-Hydroxy-11-(N-piperidyl)undecane (10.70 g., 41.89 mmole) was dissolved in 200 ml. of anhydrous methylene chloride. The solution was cooled to 0° C. with an ice bath and then treated with 4-(N,N-dimethylamino)pyridine (5.12 g., 41.91 mmole) followed by p-toluenesulfonyl chloride (7.99 g., 41.91 mmole). The reaction mixture was stirred at 0° C. for 18 hours or until all of the starting material was consumed as determined by thin layer chromatography on silica gel. When complete, the reaction mixture was washed with water, saturated aqueous sodium bicarbonate solution and saturated aqueous sodium chloride solution. The methylene chloride solution was dried over magnesium sulfate, filtered and concentrated under reduced pressure to afford 11-(N-piperidyl)undecane-1-(p-toluene)sulfonate as a viscous oil (15.81 g., 92.1% yield). ¹ H-NMR (200 MHz., CDCl₃) δ=1.10-1.75 ppm, m, 24H; 2.15-2.65, m, 6H; 2.46, s, 3H; 4.01, t, J=6.4 Hz., 2H; 7.35, d, J=8.3 Hz., 2H; 7.80, d, J=8.3 Hz., 2H. ¹ H-NMR (200 MHz., CD₃ OD) δ=1.10-1.80 ppm, m, 24H; 2.10-2.70, m, 6H; 2.46, s, 3H; 4.01, t, J=6.2 Hz, 2H; 7.44, d, J=8.2 Hz, 2H; 7.78, d, J=8.2 Hz., 2H. IR(neat) 2925, 2880, 2800, 2760, 1610, 1450, 1360, 1175, 1100, 960, 840, 670 cm⁻¹.

B. Polymerization of Poly 11-(N-piperidyl)undecane-1-(p-toluene) sulfonate

On standing over a period of 1-4 weeks, the above monomer polymerizes to form the water soluble polymeric quaternary ammonium salt: poly (11-piperidinium undecane p-toluenesulfonate). m.p. 95°-106° C.

C. Biocidal activity of poly (11-(N-piperidyl)undecane-1-(p-toluene) sulfonate) compared to commercially available quatbiocides

The poly 11-(N-piperidyl)undecane-1-(p-toluene) sulfonate exhibits unexpected outstanding biocidal efficacy in complex media in the secondary MIC/SOK test (4-16 ppm range). In a side-by-side test against commercially available quat compounds, poly 11-(N-piperidyl)undecane-1-(p-toluene) sulfonate maintained superior efficacy in the complex media (triptocase soy broth). Especially noteworthy is the Total Kill Test data for of the polymer of the invention and the fact that it is not inactivated by the presence of organic media. In none of the commercially available quats is the nitrogen atom part of a ring.

                                      TABLE 1                                      __________________________________________________________________________     MIC BIOCIDES TEST DATA (ppm)                                                           Total                          Modified                                        Kill                                                                               (G-) (G-)                                                                               (G-)                                                                               (G+) (F) (F)  Total                                   Quat    Test                                                                               PSFL PSAE                                                                               ECOL                                                                               SAUR ANIG                                                                               APUL Kill                                    __________________________________________________________________________     Example 1                                                                               4  4    16  8   4    16  4    8                                       (Invention)                                                                    Comparative A                                                                          63  >250 250 250 >250 250 >250                                         Comparative B                                                                          16  1     8  8   1    4   8                                            Comparative C                                                                          16  1    63  16  2    4   1                                            __________________________________________________________________________      Comparative A = Busan 77 ™ poly[oxyethylene (dimethyliminio) ethylene       (dimethyliminio) ethylenedichloride                                            Comparative B = Hyamine 1600 ™ alkyl dimethylbenzyl ammonium chloride       Comparative C = Hyamine 3500 ™ alkyl dimethylbenzyl ammonium chloride       Invention = Poly 11(N-piperidyl)undecane-1-(p-toluene) sulfonate         

EXAMPLE 2

Following the procedure of Examples 1 A and B except using 12-bromododecanol instead of 11-bromoundecanol, polymer 2 was prepared.

EXAMPLE 3

Following the procedure of Examples 1 A and B except using phenylsulfonyl chloride instead of p-toluene sulfonyl chloride, polymer 3 was prepared.

EXAMPLE 4

Following the procedure of Examples 1 A and B except using p-nitrophenyl sulfonyl chloride instead of p-toluene sulfonyl chloride, polymer 4 was prepared.

EXAMPLE 5

Following the procedure of Examples 1 A and B except using methane sulfonyl chloride, monomer 5 in crystilline form according to formula IV was prepared.

EXAMPLE 6

Following the procedure of Examples 1 A and B except using p-chlorophenyl sulfonyl chloride instead of p-toluene sulfonyl chloride, polymer 6 was prepared.

EXAMPLE 7

Following the procedure of Examples 1 A and B except using hexamethylene imine instead of piperidine, polymer 7 was prepared.

EXAMPLE 8

Following the procedure of Examples 1 A and B except using pyrrolidine instead of piperidine, polymer 8 was prepared.

EXAMPLE 9

Following the procedure of Examples 1 A and B except using 12-bromododecanol was used instead of 11-bromoundecanol and hexamethylene imine instead of piperidine, polymer 9 was prepared.

EXAMPLE 10

Following the procedure of Examples 1 A and B except using 12-bromododecanol and pyrrolidine, polymer 10 was prepared.

EXAMPLE 11

Following the procedure of Examples 1 A and B except using 12-bromododecanol, pyrrolidine, and phenylsulfonylchloride, polymer 11 was prepared.

EXAMPLE 12

Following the procedure of Examples 1 A and B except using 12-bromododecanol, hexamethylene imine, and phenylsulfonyl chloride, polymer 12 was prepared.

EXAMPLE 13

Following the procedure of Examples 1 A and B except using morpholine instead of piperdine, polymer 13 was prepared.

EXAMPLE 14

The polymers or monomer of Examples 2 to 13 were tested with the results reported in Table 2.

                                      TABLE 2                                      __________________________________________________________________________                                        Total                                                                          Kill Test                                                                            Modified                              MIC (ppm)                          (ppm) 4 hrs                                                                          Total Kill Test*                      Example                                                                             Psae Ecol  Saur  Anig                                                                               Apul                                                                               Chlor                                                                               Psae  10 min results                        __________________________________________________________________________      2   63   4     4     4   1     0.5                                                                               >250  16                                     3   16   8     4     8   4    <0.12                                                                              -8     8                                     4   >250 >250  8     32  16   <0.12                                                                              >250  >500                                   5   >250 >250  >250  250 125 >250 >250  >500                                   6   16   16    63    16  8   250   8     8                                     7   32   16    8     4     0.5                                                                               <0.12                                                                              16    16                                     8   16   8     16    4     0.25                                                                               0.25                                                                              16     8                                     9   32   8     4     4     0.5                                                                                0.5                                                                               125   32                                    10    4   4     2     1   1   8    32     8                                    11    4   4     2     4   2   2    16     8                                    12   63   16    8     16  8   8    250   16                                    13   >250 >250  63    63  16  --   16    --                                    __________________________________________________________________________      *to kill 2.2 × 10.sup.4 CFU in 10 min.                             

EXAMPLE 15

SOK for Examples 1 and 11 were measured with the following results in log/3 min. against Psae, Saur, and Schlo using 100 ppm of test compound.

    ______________________________________                                         SOK                                                                            Example    Psae         Saur   Schlo                                           ______________________________________                                          1         4            2      2                                               11         6            4      5                                               ______________________________________                                     

We claim:
 1. Process comprising reacting a monoalcohol of the formula

    X--R.sub.1 --OH                                            (I)

wherein R₁ =--(CH₂)_(m) --, --(CH₂ CH₂ --O)_(n) --CH₂ CH₂ --, or --(CH₂ CH₂ CH₂ --O)_(n) --CH₂ CH₂ CH₂ -- in which m=7 to 24, n=1 to 10, and wherein X=Br, Cl, or OSO₂ R wherein R is alkyl, cycloalkyl, aryl, substituted aryl, alkaryl optionally substituted on the aryl potion or aralkyl optionally substituted on the aryl portion, R having up to 20 carbon atoms and is optionally branched with a molar excess of secondary ring amine of the formula ##STR10## wherein A is (CH₂)_(p), or (CH₂)_(q--O--)(CH₂)_(r) wherein p= 4 to 6; q=2; and r=2; to form a compound of the formula ##STR11## and reacting (III) with X'SO2R wherein R is alkyl, cycloalkyl, aryl, substituted aryl, alkaryl optionally substituted on the aryl potion or aralkyl optionally substituted on the aryl portion, R having up to 20 carbon atoms and is optionally branched and wherein X' is Cl or Br, to produce a monomer of the formula ##STR12##
 2. Compounds having the formula (IV). 